Evacuation of hydrogen and carbon monoxide from a hydrocarbonaceous feedstock

ABSTRACT

A catalyst comprising a catalytically active metal, selected from Ru, Rh, Os and Ir, associated with at least one inorganic metal cation or precursor thereof, wherein the inorganic metal cation or precursor thereof is present in intimate association supported on or with the catalytically active metal, a process for the preparation of the catalyst, and a process for the preparation of carbon monoxide and/or hydrogen from a hydrocarbonaceous feedstock using the catalyst.

The present invention relates to a catalyst suitable for the preparationof carbon monoxide and/or hydrogen from a gaseous or liquidhydrocarbonaceous feedstock, a process for the preparation of such acatalyst, and a catalytic partial oxidation process using such acatalyst.

The partial oxidation of hydrocarbons, for example methane or naturalgas, in the presence of a catalyst is an attractive route for thepreparation of synthesis gas. The partial oxidation of a hydrocarbon isan exothermic reaction and, in the case in which methane is thehydrocarbon, proceeds by the following reaction:

2CH₄+O₂→2CO+4H₂

The optimum catalytic partial oxidation process for application on acommercial scale would give high yields of carbon monoxide and hydrogenat elevated pressures, for example about 30 bar, and high spacevelocities, for example of the order of 1,000,000 Nl/kg/h or more. Forthermodynamic reasons, in order to obtain high yields of carbon monoxideand hydrogen under these process conditions, it is necessary to operatethe partial oxidation process at high temperatures.

The literature contains a number of documents disclosing details ofexperiments conducted into the catalytic oxidation of hydrocarbons, inparticular methane, employing a wide range of catalysts. Reference ismade for instance to U.S. Pat. No. 5,149,464, WO 92/11199, and WO93/01130. The majority of these experiments, however, have beenconducted under relatively mild conditions or under conditions unsuitedto the operation of a large, commercial catalytic partial oxidationprocess.

The literature, moreover, contains a number of documents disclosingdetails of experiments conducted into the catalytic partial oxidation ofhydrocarbons under conditions required for commercial operation toproduce mixtures of carbon monoxide and/or hydrogen.

In EP-A-640561 is disclosed that the catalytic partial oxidation processmay be operated under conditions demanded of commercial processes, inhigh yield and with low deactivation by employing a catalyst comprisinga Group VIII catalytically active metal supported on a refractory oxidehaving at least two cations selected from Groups IA, IIA, IIIA and IVAof the Periodic Table or the transition metals.

Moreover, in EP-A-737164 is disclosed that, when operated under theconditions of elevated pressure and at high temperature as demanded by acommercial process, the catalytic partial oxidation of hydrocarbons can,in the presence of nitrogen, yield a synthesis gas product containing anumber of by-products, in particular ammonia (NH₃) and hydrogen cyanide(HCN), in low but significant amounts. It has been found that suchby-products can adversely affect downstream processes to convert thecarbon monoxide and/or hydrogen produced by the catalytic partialoxidation process, e.g. in the case of Fischer-Tropsch synthesis or ofthe synthesis of methanol. The presence of by-products, in particularammonia or hydrogen cyanide, in the products of the catalytic partialoxidation process is thus undesirable. In EP-A-737164 is disclosed thatthe generation of such by-products is significantly lower in a processemploying a catalyst comprising rhodium, iridium or platinum ascatalytically active metal. At such levels it is possible to remove anyundesired by-products, using known solvent, absorption processes and thelike. Alpha-alumina is employed as the catalyst support.

In WO 96/04200 is disclosed a catalytic partial oxidation process whichemploys a Group VIII catalytically active metal supported on azirconia-based carrier, which is found to have a high thermal-shockresistance.

In EP 548 679 is disclosed a catalytic partial oxidation process whereina catalyst containing ruthenium and/or rhodium as an active ingredientand cobalt and/or manganese as a promoter is used.

Accordingly, it will be apparent that there are a number of conditionsand circumstances which affect the performance of a catalytic partialoxidation reaction, and that whilst it is possible to optimize in termsof individual performance parameters, there is some conflict betweenindividual optimizations, each directed specifically to one of the aboveperformance parameters, whereby it is not possible to operate a processwith simultaneous optimization of all conditions. Specifically, nitrogenis present in many natural gas feedstocks, and the preparation of pure,nitrogen-free oxygen on a commercial scale is both very expensive andtechnically difficult. Therefore the process must produce acceptably lowlevels of N-containing by-product. Moreover, the choice of catalyticallyactive metal, refractory oxide and the like in the catalyst to beeffective on a commercial scale must be made bearing in mind factorsincluding high temperature and pressure resistance and thermal-shockresistane under the extreme conditions to be employed in terms of thefactors hereinbefore mentioned. Finally, the process must produceoptimum yields and selectivity to desired products and optimum lifetimeunder such extreme conditions, and indeed under varying conditions whichmay prevail in the event of fluctuations in operation.

Accordingly, there is a need for a process for the catalytic partialoxidation of hydrocarbons in which nitrogen may be present during thepartial oxidation reactions, which may be applied on a commercial scaleto produce a product of carbon monoxide and/or hydrogen in high yieldand selectivity, containing a minimum of components such as ammonia andhydrogen cyanide, and at low or negligible catalyst deactivation rates.

Surprisingly, it has been found that, by employing in the catalyticpartial oxidation process a catalyst comprising the catalytically activemetal associated with a performance modifying cation selected.from Al,Mg, Zr, Ti, La, Hf, and Si, the above objects may be achieved inadmirable manner, for a wide range of operating conditions. Moreover,selection of cation employed may be made for optimization of specificperformance factors, including feedstock conversion and product yield,catalyst stability, coke formation, top temperature control and thelike.

Accordingly, the present invention provides a catalyst comprising acatalytically active metal, selected from Ru, Rh, Os and Ir, associatedwith a metal cation selected from Al, Mg, Zr, Ti, La, Hf, and Sisupported on a carrier, obtainable by a process comprising providing themetal cation and the catalytically active metal in solutions adapted forimpregnation or co-impregnation on the carrier, drying, and optionallycalcining.

The inorganic metal cation is selected from Al, Mg, Zr, Ti, La, Hf, andSi, of which Zr is preferred. The cation is preferably in the form ofits oxide.

The catalyst is supported on a carrier, for example comprising arefractory oxide having at least one cation, or comprising a metal orother attrition resistant, high temperature resistant substrate.

Preferably, the catalyst comprises cation to metal in an atomic ratio inexcess of or equal to 1.0 at its surface, more preferably in excess ofor equal to 2.0, even more preferably in excess of or equal to 3.0 up toa maximum only limited by the constraints of the method for constructingthe catalyst, e.g. impregnation.

It is a particular advantage of the catalyst of the present inventionthat the nature of association of the catalytically active metal and themetal cation would seem to be at least partially self-regulating ordirecting. Without being limited to this theory it would seem that aform of feedstock conditioning by the metal cation serves to optimizecatalytic activity and thereby generate enhancement in the performanceparameters of yield, selectivity, deactivation resistance and lowby-product formation simultaneously.

The catalytically active metal is selected from ruthenium, rhodium,osmium and iridium, preferably from rhodium and iridium. As has beendiscussed hereinbefore, these metals offer the significant advantagethat substantially lower amounts of ammonia and hydrogen cyanide areproduced during the catalytic partial oxidation reaction, compared withthe other metals from Group VIII of the Periodic Table of the Elements.

The catalyst may comprise the catalytically active metal in any suitableamount to achieve the required level of activity. Typically, thecatalyst comprises the active metal in an amount in the range of from0.01 to 20% by weight, preferably from 0.02 to 10% by weight, morepreferably from 0.1 to 7.5% by weight.

The catalyst may comprise the metal cation in any suitable amount toachieve the required level of selectivity and conversion anddeactivation resistance. Typically the catalyst comprises the metalcation in an amount of at least 0.5 weight %. The cation is preferablypresent in the catalyst in a range of from 1.5-15.0 weight %, mostpreferably 5.0 to 15.0 weight %.

The catalytically active metal is supported on a carrier. Suitablecarrier materials are well known in the art and include the refractoryoxides, such as silica, alumina, titania, zirconia and mixtures thereof.Mixed refractory oxides, that is refractory oxides comprising at leasttwo cations may also be employed as carrier materials for the catalyst.Most suitable refractory oxide carriers are binary oxides of zirconiaand alumina, in particular in (partially) stabilised form such as ZTA(zirconia toughened alumina) or PSZ (partially stabilised zirconia),mullite or alumina. Also metals or metal alloys, for examplefecralloy-type alloys, preferably in the form of gauzes, can be suitablyapplied as carrier material.

A suitable technique for associating the metal and metal cation isimpregnation, in the case that the metal and cation are supported on acarrier as hereinbefore is defined. Preferably, the carrier isimpregnated with a solution of a compound of the catalytically activemetal and a solution of a salt of the metal cation, followed by dryingand, optionally, calcining the resulting material. The solutions arepreferably combined in suitable amount and co-impregnated. Alternativelyimpregnation may be sequential, with the first stage impregnation,drying and, optionally, calcining with the catalytically active metalsolution, and second stage impregnation, drying and, optionally,calcining with the metal cation solution or a mixture thereof with thecatalytically active metal solution.

Preferred techniques for impregnation are by dipping, painting,spraying, immersing, applying by measured droplet and the like of asuspension or solution of the modifying cation, with subsequent dryingin hot air or the like and calcining, in manner that a uniformimpregnation is achieved. Preferably, impregnation and/or drying iscarried out in the absence of distorting gravitation, meniscus orcapillary effects during drying, which might provide an undesiredgradient or total content of the impregnated cation. For example, theoxide support may be rotated or suspended in manner that contact withany other objects does not encourage meniscus or capillary effects.

Accordingly, in a further aspect of the invention there is provided aprocess for the preparation of a catalyst adapted to catalyze a partialoxidation reaction, the catalyst comprising a catalytically activemetal, selected from Ru, Rh, Os and Ir, associated with a metal cationselected from Al, Mg, Zr, Ti, La, Hf, and Si supported on a carrier, theprocess comprising providing the metal cation and the catalyticallyactive metal in solutions adapted for impregnation or co-impregnation onthe carrier, drying, and optionally calcining.

In a further aspect of the invention there is provided a process for thepreparation of carbon monoxide and/or hydrogen from a hydrocarbonaceousfeedstock, which process comprises contacting a mixture of the feedstockand an oxygen-containing gas with a catalyst comprising a catalyticallyactive metal, selected from Ru, Rh, Os and Ir, associated with a metalcation selected from Al, Mg, Zr, Ti, La, Hf, and Si supported on acarrier, obtainable by a process comprising providing the metal cationand the catalytically active metal in solutions adapted for impregnationor co-impregnation on the carrier, drying, and optionally calcining.

The process of the present invention may be used to prepare carbonmonoxide and/or hydrogen from any hydrocarbonaceous feedstock that isgaseous under the conditions prevailing during the partial oxidationreaction. The feedstock may contain compounds that are liquid and/orcompounds that are gaseous under standard conditions of temperature andpressure (i.e. at 0° C. and 1 atm.). The process is particularlysuitable for the conversion of methane, natural gas, associated gas orother sources of light hydrocarbons. In this respect, the term “lighthydrocarbons” is a reference to hydrocarbons having from 1 to 5 carbonatoms. The process may be applied in the conversion of naturallyoccurring reserves of methane which contain a substantial amount ofcarbon dioxide. The feed preferably comprises methane in an amount of atleast 50% by volume, more preferably at least 75% by volume, especiallyat least 80% by volume. The process is also particularly suitable forthe conversion of liquid hydrocarbon feedstocks such as naphthafeedstocks boiling between 35° C. and 150° C., kerosene feedstocksboiling between 150° C. and 200° C., synthetic gas oil feedstocksboiling between 200° C. and 500° C., in particular between 200° C. and300° C.

It is possible to have hydrocarbonaceous material present in thefeedstocks to be used in the process according to the present inventionwhich are gaseous under standard conditions of temperature and pressure,together with material which are liquid under standard conditions oftemperature and pressure. Hydrocarbons which are liquid under standardconditions of temperature and pressure typically contain up to 25 carbonatoms in their molecules.

The process according to the present invention can also be carried outwhen the feedstock contains oxygenates (being gaseous and/or beingliquid under standard condition of temperature and pressure). Oxygenatesto be used as (part of) the feedstock in the process according to thepresent invention are defined as molecules containing apart from carbonand hydrogen atoms at least 1 oxygen atom which is linked to either oneor two carbon atoms or to a carbon atom and a hydrogen atom. Examples ofsuitable oxygenates comprise methanol, ethanol, dimethyl ether andalkanols, ether, acids and esters having up to 25 carbon atoms.

Also mixtures of hydrocarbons and oxygenates as defined hereinbefore canbe used as feedstock in the process according to the present invention.

The hydrocarbonaceous feedstock is contacted with an oxygen-containinggas during the partial oxidation process. Air may be used as theoxygen-containing gas, in which case nitrogen will be present in thefeed and reaction mixture in large quantities. Alternatively,substantially pure oxygen or oxygen-enriched air may be used.

Preferably, the feed comprises the hydrocarbonaceous feedstock andoxygen in amounts giving an oxygen-to-carbon ratio in the range of from0.3 to 0.8, preferably from 0.45 to 0.75. References to theoxygen-to-carbon ratio refer to the ratio of oxygen in the form ofmolecules (O₂) to carbon atoms present in the hydrocarbon feedstock.Oxygen-to-carbon ratios of the stoichiometric ratio, 0.5, that is in therange of from 0.45 to 0.65, are particularly suitable.

If oxygenate feedstocks are used, e.g. methanol, oxygen-to-carbon ratiosbelow 0.3 can suitably be used.

The feed may optionally comprise steam. If steam is present in the feed,the steam-to-carbon ratio (that is the ratio of molecules of steam (H₂O)to carbon atoms in the hydrocarbon) is preferably in the range of fromabove 0.0 to 3.0, more preferably from above 0.0 to 2.0.

The process of the present invention is operated at elevated pressures,that is pressures significantly above atmospheric pressure. The processis typically operated at pressures in the range of up to 150 bara.Preferably, the operating pressure is in the range of from 2 to 125bara, more preferably from 5 to 100 bara.

The process may be operated at any suitable temperature. Under thepreferred conditions of high pressure prevailing in the process, thefeed gases are typically allowed to contact the catalyst at elevatedtemperatures in order to achieve the level of conversion required for acommercial scale operation. Accordingly, the process is typicallyoperated at a temperature of at least 750° C. Preferably, the operatingtemperature is in the range of from 800 to 1300° C., more preferably inthe range of from 900 to 1200° C. Temperatures in the range of from 1000to 1200° C. are particularly suitable with substantially pure oxygen, orin the range of from 800° C. to 1000° C. with air. Reference herein totemperature is to the temperature of the gas leaving the catalyst.

The feed mixture is typically provided during the catalytic partialoxidation process at gas space velocities (expressed as normal leters(i.e. leters at 0° C. and 1 atm.) of gas per kilogram of catalyst perhour) in the range of from 20,000 to 100,000,000 Nl/kg/h, preferably inthe range of from 50,000 to 50,000,000 Nl/kg/h. Space velocities in therange of from 500,000 to 30,000,000 Nl/kg/h are particularly suitable.

The gaseous mixture of the hydrocarbonaceous feedstock and theoxygen-containing gas is preferably contacted with the catalyst underadiabatic conditions. For the purposes of this specification, the term“adiabatic” is a reference to reaction conditions in which substantiallyall heat loss and radiation from the reaction zone is prevented, withthe exception of heat leaving in the gaseous effluent stream of thereactor.

Any suitable reaction regime may be applied in the process of thepresent invention in order to contact the reactants with the catalyst.One suitable regime is a fluidized bed, in which the catalyst isemployed in the form of particles fluidized by a stream of gas. Apreferred reaction regime for use in the process is a fixed bed reactionregime, in which the catalyst is retained within a reaction zone in afixed arrangement. Particles of catalyst may be employed in the fixedbed regime, retained using fixed bed reaction techniques well known inthe art. Alternatively, the fixed arrangement may comprise the catalystin the form of a monolithic structure. A most preferred monolithicstructure comprises a ceramic foam. Suitable ceramic foams for use inthe process are available commercially. Further, alternative forms forthe catalyst include refractory oxide honeycomb monolith structures ormetal gauze structures.

A mixture of carbon monoxide and hydrogen prepared by the process ofthis invention is particularly suitable for use in the synthesis ofhydrocarbons, for example by means of the Fisher-Tropsch synthesis, orthe synthesis of oxygenates, for example methanol. Processes for theconversion of the mixture of carbon monoxide and hydrogen into suchproducts are well known in the art.

Hydrogen or a mixture with other gases, prepared by the process of thisinvention may be particularly suitable for use as a combustible fueleither directly or indirectly.

The process of this invention could very suitably be used to provide thehydrogen feed for a fuel cell. In fuel cells, hydrogen and oxygen arepassed over the fuel cell in order to produce electricity and water.Fuel cell technology is well known in the art.

The present invention is further described by way of the followingillustrative examples.

EXAMPLE 1 Catalyst Preparation—not According to the Invention

1600 pp cm⁻² (pores per cm²) ceramic foam was cut to size to fit intothe reactor or was crushed and sieved to 30/80 mesh particles beforeplacing in an oven at 120° C. over night. Foam (particles) was weighedand the amount of rhodium or iridium chloride solution needed to give a5 wt % rhodium or iridium loading was calculated. The solution was addedto the foam (particles) to impregnate them in three steps and the foam(particles) were dried in an oven at 140° C. in between eachimpregnation. This was repeated until all the necessary amount ofsolution was added. After this the foam (particles) were dried andcalcined in air as follows: 4 hours at 120° C., temperature raised to700° C. with 80° C./hour, 4 hours at 700° C. and cool-down to 120° C.

The resulting catalysts comprised 5.0 weight % of iridium or rhodium onPSZ (partially-stabilised zirconia), ZTA (zirconia-toughened alumina),alumina or mullite foam. The results are given in Table 1.

EXAMPLE 2 Catalyst Preparation—According to the Invention

The procedure of Example 1 was followed with the exception that theimpregnating solution was modified by addition of a solution of a saltof an inorganic cation calculated to give a 5 weight % loading of theinorganic cations. Solutions were selected from zirconyl nitrate, Mgnitrate, Al nitrate, and their mixtures.

The resulting catalysts comprised 5.0% by weight iridium or rhodium and5% by weight of cations of Zr, Mg, Al, or Mg—Al, co-impregnated on 1600ppcm⁻² PSZ, ZTA, alumina, or mullite foam. The results are given inTable 2.

EXAMPLE 3 Catalyst Preparation—According to the Invention

The procedure of Example 1 was followed with the additional stage of asecond impregnation using a solution of a salt of an inorganic metalcation calculated to give a 5 weight % loading of the inorganic metalcation. The second impregnation was carried out using the same procedureof Example 1 for the first impregnation. The resulting impregnated foam(particles) were calcined using the procedure of Example 1.

The resulting catalysts comprised 5.0% by weight Ir or Rh and 5% byweight of cations of Zr, sequentially impregnated on alumina or Y-PSZfoam.

The results are given in Table 3.

TABLE 1 Catalyst Foam Group VIII Metal Metal Cation 1a Y-PSZ Ir — 1bAlumina Ir — 1c Y-PSZ Rh — 1d Ce-ZTA Ir — 1e ZTA Ir — 1f Zr-mullite Ir —

TABLE 2 Catalyst Foam Group VIII Metal Metal Cation 2a Y-PSZ Ir Zrco-impreg 2b Y-PSZ Ir Mg co-impreg 2c Y-PSZ Ir Al co-impreg 2d Y-PSZ IrMgAl co-impreg 2e Y-PSZ Rh Zr co-impreg 2f Alumina Ir Zr co-impreg 2gCe-ZTA Ir Zr co-impreg 2h ZTA Ir Zr co-impreg 2I mullite Ir Zr co-impreg

TABLE 3 Catalyst Foam Group VIII Metal Metal Cation 3a Alumina Ir Zrseq. impreg 3b Y-PSZ Ir Zr seq. impreg

EXAMPLE 4 Catalytic Partial Oxidation

A reactor was constructed comprising a transparent sapphire or metaltube. The modified catalyst prepared as hereinbefore described wasloaded into the tube and retained in the form of a fixed bed ofcatalyst. Methane and air or oxygen-enriched air (O₂:N₂ is 1.8 v/v), insufficient amounts to give an oxygen-to-carbon ratio in the range offrom 0.49 to 0.64, were thoroughly mixed just before being introducedinto the reactor to contact the fixed bed of catalyst. The mixture ofmethane and air or oxygen-enriched air was fed to the reactor at apressure of 11 bara and at a gas hourly space velocity (GHSV) in therange of from 2,500,000 to 3,600,000 Nl/kg/h.

The composition of the gas mixture leaving the reactor was determined bygas chromatography and weighing water condensed from the gas streamleaving the reactor.

In Tables 4 to 7 are given the results as xCH₄ (% methane conversion),sCO, and sH₂ (selectivity to CO and H₂)

TABLE 4 Enriched-air CPO: Performance of Ir/Y-PSZ with metal cation(GHSV is 3,300,000 Nl/kg/h; O₂:C is 0.55) xCH₄ sCO sH₂ NH₃ make Catalyst% % % ppmv 1a 88 95 88 0.5 2a 91 95 90 0.5 2b 92 95 91 0.8 2c 92 95 911.1 2d 92 95 93 1.0 Thermo^(a) 93 95 93 230 ^(a)Performance atthermodynamic equilibrium

TABLE 5 Enriched-air-CPC: Effect of modifier on Ir/Y-PSZ (GHSV is3,400,000 Nl/kg/h; O₂:C is 0.63) xCH₄ sCO sH₂ NH₃ make Deact.^(b)Catalyst % % % ppmv %/24 hour 1a 98 95 88 1.6 3 2a 99 95 88 2.1 0.5Thermo 99.7 95 89 113 ^(b)Decline in xCH₄ per 24h

The results presented in Table 4 and 5 indicate that the modifiers havea beneficial influence on the CH₄ conversion. The important parametersof the catalyst performance are: a high CH₄ conversion, a low NH₃ makeand a high stability. The stability is expressed as the decrease in CH₄conversion as function of time. The zirconia modifier appeared to bemost beneficial: the CH₄ conversion of this catalyst was the highestwhile at the same time the NH₃ make was not much increased. Thiscatalyst was tested for its stability and it appeared higher than thestability of the catalyst without modifier.

The Zr modification of CPO catalysts is not only beneficial for theY-PSZ supported catalysts. An even stronger effect is observed with analumina support. The Ir/alumina catalyst was not active in theenriched-air-CPO experiment, while the Zr-modified Ir/alumina showed anexcellent performance. A high and stable CH₄ conversion was measured(see Table 6).

TABLE 6 Enriched-air-CPO: Performance of Ir/alumina (alumina: DytechPoral 20; GHSV is 4,900,000 Nl/kg/h; O₂:C is 0.63) XCH₄ SCO SH₂ Deact.Catalyst % % % %/24 hour 1b No reaction 2f 99 95 88 0.6 3a 99 95 89 1.8Thermo 99.4 95 90

Of interest are the air-CPO experiments. It appeared that also underthese conditions the Zr modification shows its benefits. Catalysts havebeen prepared with differing active phases and different supports andthe results show an improved performance of most systems when the Zrmodification is applied (see Table 7). Zr-modified catalysts show ahigher CH₄ conversion, whilst the NH₃ make is not much increased.

In Table 7, 1a, and 1c-1f represent catalysts not according to theinvention, given for comparative purpose with corresponding catalystsaccording to the invention.

In the process using catalyst 3b, prepared by. impregnating a solutionof zirconia on Ir/Y-PSZ, the presence of zirconia improves theperformance of the catalyst, without changing the Ir dispersion.However, the catalyst prepared in this way is not as good as thecatalyst in which the Ir and Zr are mixed in the impregnation solution.

TABLE 7 Air-CPO: Effect of Zr on different supports (GHSV is 3,400,000Nl/kg/h; O₂:C is 0.49) xCH₄ sCO sH₂ Catalyst % % % 1c (comp) 64 88 79 2e75 90 88 1a (comp) 65 88 80 2a 74 90 88 3b 68 88 80 1d (comp) 63 87 792g 75 90 88 1e (comp) 60 85 75 2h 74 90 86 1f (comp) 70 89 85 2I 72 8985 Thermo 74 90 90

What is claimed is:
 1. A process for the preparation of carbon monoxideand hydrogen from a hydrocarbonaceous feedstock, which process comprisescontacting a mixture of the feedstock and an oxygen-containing gas witha catalyst comprising a catalytically active metal, selected from thegroup consisting of Ru, Rh, Os and Ir, associated with a metal cationselected from the group consisting of Al, Mg, Zr, Ti, La, Hf, and Sisupported on a carrier, said catalyst prepared by a process comprising:providing the metal cation and the catalytically active metal insolutions adapted for impregnation or co-impregnation on the carrier;drying; and, optionally calcining; wherein the mixture is contacted withthe catalyst at a temperature of at least about 750° C., at a pressureof up to about 150 bara, and at a gas hourly space velocity in the rangeof from about 20,000 Nl/kg/h to about 100,000,000 Nl/kg/h.
 2. Theprocess of claim 1 in which the mixture is contacted with the catalystat a temperature of at least about 750° C., at a pressure of up to about150 bara, and at a gas hourly space velocity in the range of from about20,000 Nl/kg/h to about 100,000,000 Nl/kg/h.
 3. The process of claim 1in which the mixture has an oxygen-to-carbon ratio in the range of fromabout 0.3 to about 0.8.
 4. The process of claim 1 in which the mixtureis contacted with the catalyst under substantially adiabatic conditions.5. The process of claim 1, in which the temperature is in the range offrom about 900° C. to about 1200° C., the pressure is in the range offrom about 5 bara to about 100 bara and the gas hourly space velocity isin the range of from about 500,000 Nl/kg/h to about 30,000,000 Nl/kg/h.6. The process of claim 5, in which the hydrocarbonaceous feedstockcomprises methane in an amount of at least 50% by volume.
 7. The processof claim 5, further comprising feeding the hydrogen into a fuel cell. 8.The process of claim 5, further comprising synthesizing hydrocarbonsfrom a reaction mixture comprising the carbon monoxide and the hydrogen.9. The process of claim 5, further comprising synthesizing oxygenatesfrom a reaction mixture comprising the carbon monoxide and the hydrogen.10. The process of claim 1, in which the hydrocarbonaceous feedstockcomprises hydrocarbons having from 1 to 5 carbon atoms.
 11. The processof claim 1, in which the hydrocarbonaceous feedstock comprises methanein an amount of at least 50% by volume.
 12. The process of claim 1, inwhich the hydrocarbonaceous feedstock comprises naphtha feedstocksboiling between about 35° C. and about 150° C.
 13. The process of claim1, in which the hydrocarbonaceous feedstock comprises kerosenefeedstocks boiling between about 150° C. and about 200° C.
 14. Theprocess of claim 1, in which the hydrocarbonaceous feedstock comprisessynthetic gas oil feedstocks boiling between about 200° C. and about300° C.
 15. The process of claim 1, in which the process is performed ina fluidized bed.
 16. The process of claim 1, in which the process isperformed in a fixed bed.
 17. The process of claim 16, in which thefixed bed comprises the catalyst in a form selected from the groupconsisting of a monolithic structure, a refractory oxide honeycombmonolith structure and a metal gauze.
 18. The process of claim 16, inwhich the fixed bed comprises the catalyst in the form of a monolithicstructure.
 19. The process of claim 18, in which the monolithicstructure is a ceramic foam.